CN107629086A - A kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants - Google Patents
A kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants Download PDFInfo
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Abstract
The invention belongs to application project plastics arts, and in particular to a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants.This method is to be reacted under louis catalyst effect using phenol with POCl3, decompression steams unnecessary POCl3, obtain mixture intermediate, mixture intermediate is carried out in condensation reaction with hydroquinones, first reacted using mixing intermediate with appropriate hydroquinones, the high vacuum dehydrochlorination after the reaction completely of part hydroquinones, reacted again plus under triethylamine and remaining hydroquinones lower temperature, the rise of low triphenyl phosphate content is greatly dropped, reduce the murder by poisoning to human body, the purity and yield of product are improved simultaneously, its technological operation is easy, it is with short production cycle, it is economic and environment-friendly, the requirement of industrial scale production can be met, suitable for industrial application.
Description
Technical field
The invention belongs to fine chemistry industry production technical field, and in particular to a kind of low triphenyl phosphate engineering plastics Halogen resistance
Fire the preparation method of agent.
Background technology
Halogen armaticity phosphoric acid ester hinders right agent because with efficient convenient fire resistance, the market space is very big, with
Rapid growth is increased production capacity by the market demand of phosphate flame retardant, the bigger industrialization rule of its formation of the right to use
Mould, meet the market demand, take part in international competition, turn into the task of top priority.
The patent CN200810063129 of traditional our company's invention uses POCl3 with first reacting biphenol, Ran Houyu
Phenol carries out the oligomer that obtains of condensation reaction, and pyrocondensation reaction could completely, and the process of high temperature easily produces disproportionation,
React and the larger triphenyl phosphate of toxicity is produced in preparation process, and the process of high temperature, the color of product easily deepen.Our company is sent out
Bright patent CN201510517986, CN201510517984 prepare low triphenyl phosphate technique BDP techniques, and triphenyl phosphate contains
Amount is less than 3%, is all to be reacted using POCl3 and Resorcino, the method for last phenol pyrocondensation, POCl3 is except clean
Method achieve the goal.In order to overcome the shortcomings that above-mentioned, using the new synthetic route preparation method of invention, first POCl3 and benzene
Phenol carries out esterification and prepares mixture intermediate, and mixture intermediate carries out condensation reaction, reaction prior to part hydroquinones
Dehydrochlorination afterwards, then add under organic base and remaining hydroquinones lower temperature and reacted.Avoid the disproportionation of high temperature anti-
Should, the larger triphenyl phosphate content of toxicity is controlled, condensation reaction is carried out at relatively low temperature, solves the color of product, and phosphoric acid
Triphenylmethyl methacrylate control is less than less than 1%.Instant invention overcomes deficiency of the prior art, there is provided it is a kind of with short production cycle, economical and
Environmental protection meets the requirement of commercial scale, rational preparation method, and the hydroquinones bis phosphoric acid phenyl ester being prepared by it is neat
Copolymer product quality gets a greater increase.
The content of the invention
The defects of occurring for product made from traditional hydroquinones bis phosphoric acid phenyl ester oligomer preparation method, the present invention carries
For a kind of preparation method of new low triphenyl phosphate engineering plastics halogen-free flame retardants, this method is easy to operate, reaction temperature is low,
Requirement that is economic and environment-friendly, can meeting industrial scale production, concrete technical scheme elder generation POCl3 of the invention are carried out with phenol
Esterification prepares mixture intermediate, and mixture intermediate first carries out condensation reaction, dechlorination after reaction with part hydroquinones
Change hydrogen, then add under organic base and remaining hydroquinones lower temperature and carry out condensation reaction.
The preparation method of described a kind of low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that by trichlorine oxygen
Phosphorus carries out reaction under lewis acid catalyst effect with phenol and prepares mixture intermediate, and mixture intermediate is right with part again
Benzenediol carry out condensation reaction, after hydroquinones reaction completely after high vacuum removing hydrogen chloride, added after take off organic base with
Remaining hydroquinones carries out condensation reaction at low temperature, and after reaction terminates, cooling, solidification obtain crude product, and crude product is located after crushing
Reason neutralizes washing, drying obtains the low triphenyl phosphate engineering plastics halogen-free flame retardants of finished product, its chemical equation through washing
It is as follows：
0≤n≤6 in above formula, n=1 therein, 2,3,4,5,6 finished product contain different contents, and the weight/mass percentage composition of n=0 is less than
Compound during 1%, n=0 is triphenyl phosphate.
The preparation method of described a kind of low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that including as follows
Step：
1）Esterif iotacation step：POCl3 and phenol are subjected to esterification to without hydrogen chloride under the catalysis of lewis acid catalyst
Untill releasing, remove under reduced pressure and reclaim POCl3, obtain a substitution of POCl3 and dibasic mixture intermediate；
2）Condensation polymerization step：Under the catalysis of lewis acid catalyst, first plus part hydroquinones is added to step 1）It is mixed
To close and primary condensation polymerisation is carried out in intermediate, the content for detecting hydroquinones extremely reacts complete, dehydrochlorination under vacuum, then
Add organic base and remaining hydroquinones progress secondary condensation polymerisation complete to intermediate reaction is mixed, obtain being esterified thick production
Thing；
3）Purification step：By step 2）Obtained esterification crude product is through cooling down, solidifying, pulverization process, and the product after crushing is through water
Wash, alkali cleaning, washing, drying obtain the low triphenyl phosphate engineering plastics halogen-free flame retardants of finished product.
A kind of preparation method of described low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that step 1）In
Esterification reaction temperature be 80-90 DEG C, preferably 85-90 DEG C, the reaction time is 3-10 hours, preferably 4-6 hours.
A kind of preparation method of described low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that step 1）In
The molar ratio of POCl3 and phenol is 1：0.8-1.5, preferably 1:1 is evaporated under reduced pressure except remaining a small amount of POCl3
Temperature is 90~120 DEG C, and preferably 85-90 DEG C of vacuum is 30~60KPa.
A kind of preparation method of described low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that step 1）With
Step 2）In lewis acid catalyst be respectively titanium tetrachloride, alchlor or magnesium chloride, preferably magnesium chloride, catalyst is used
Measure the 0.001-0.5% of the weight for POCl3, preferably 0.01%.
A kind of preparation method of described low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that step 2）In
The molar ratio of mixture intermediate and total hydroquinones be 1：1.1-2.0 preferably 1：1.5 moles, primary condensation is gathered
The hydroquinones put into during conjunction accounts for the 55-65% of total amount, preferably 60%, and the hydroquinones that secondary condensation is put into when polymerizeing accounts for total amount
35-45%, preferably 40%, primary condensation polymeric reaction temperature is 100~150 DEG C, preferably 140 DEG C, once comprehensive polymerization
Time is 3-10 hours, preferably 3-5 hours.
A kind of preparation method of described low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that step 2）Middle dechlorination
It is 60~100 DEG C to change hydrogen temperature, and preferably 65-90 DEG C, vacuum is 30~60KPa.
A kind of preparation method of described low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that step 2）In
Organic base be triethylamine, diethylamine, ammonia or pyridine, preferably triethylamine, the amount for adding organic base is mixture intermediate
The 2-5% of weight, preferably 2%.
A kind of preparation method of described low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that step 2）In
Except the secondary condensation polymeric reaction temperature after de-chlorine hydride is 60~100 DEG C, preferably 80-90 DEG C, the reaction time is that 4-13 is small
When, preferably 4-10 hours.
A kind of preparation method of described low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that step 3）In
Using alkaline weak solution alkali cleaning, alkaline weak solution is any in sodium hydroxide solution, sodium carbonate liquor or sodium bicarbonate solution
One kind, preferably sodium hydroxide solution, the mass concentration 3~5% of alkaline weak solution, alkali cleaning temperature are 60~80 DEG C, the alkali cleaning time
For 25-35min, preferably 30min, water is separated, is then washed to neutrality.
POCl3 and phenol are first carried out esterification preparation and mix intermediate by using above-mentioned technology by the present invention,
Mix intermediate and first carry out condensation reaction with part hydroquinones, dehydrochlorination after reaction, then add organic base and remaining
Condensation reaction is carried out under hydroquinones lower temperature, it is post-treated to obtain low triphenyl phosphate engineering plastics halogen-free flame retardants.This hair
It is bright it is easy to operate, reaction temperature is low, it is with short production cycle, economic and environment-friendly, can meet industrial scale production requirement, obtained production
Product purity is high, and triphenyl phosphate content greatly reduces, suitable for industrial application.
Embodiment
The invention will be further described with reference to embodiments, but protection scope of the present invention is not limited to that：
Embodiment 1：
Respectively by 78g（0.5mol）POCl3, magnesium chloride 0.1g, which is added in four-hole boiling flask, rises to temperature as 70-80 DEG C, slowly
50g (0.55mol) phenol is added dropwise, time for adding is 2.5 hours, in 80-90 DEG C of insulation reaction 5 hours after dripping, to without chlorine
After changing hydrogen releasing, reaction is completed, and it is 30-100KPa, vapo(u)rizing temperature 30-100 that POCl3 vacuum is evaporated under reduced pressure after reaction
DEG C, mixture intermediate is obtained after vacuum distillation, i.e. a substitution of POCl3 and dibasic mixture, a substitution and two takes
Ratio for mixture is 4:6, the yield 95% of mixture intermediate, the rate of recovery of POCl3 is 95%（In terms of POCl3
Calculate）；
Mixture intermediate is added in four-hole boiling flask, adds magnesium chloride 0.1g, hydroquinones 60g is first added, is to slowly warm up to
130-140 DEG C reaction, the reaction time be 6 hours, to without hydrogen chloride release after, be evaporated under reduced pressure deacidification, vacuum be 30-
60KPa, decompression temperature are 85-90 DEG C, and decompression removes hydrogen chloride 1 hour, then triethylamine 20g is slowly added dropwise, and feed liquid is neutrality, is added
Remaining hydroquinones 20g is reacted, and reaction temperature is 90-100 DEG C, and the reaction time is 4 hours, and liquid phase detection intermediate is anti-
Should be complete.Reaction is poured out liquid cooling solidification and smashed after terminating, the solid 100g after smashing is added into 150g water, with the hydrogen of 30g 3%
Sodium hydroxide solution is washed, and then washing is neutral, and material drying smashing obtains finished product, the total recovery about 93% of two-step reaction, melts
Point：100-103 DEG C, triphenyl phosphate accounts for the 0.5% of total amount, obtains white crystalline powder.
Contrast test test example 1
Respectively by 78g（0.5mol）POCl3, magnesium chloride 0.1g, which is added in four-hole boiling flask, to be reacted, and it is 70- to rise to temperature
80 DEG C, phenol 50g (0.55mol) phenol, time for adding 2-3 hours, in 80-90 DEG C of insulation reaction 3- after dripping slowly is added dropwise
5 hours, to after being released without hydrogen chloride, reaction was completed, and it is 30-100KPa that POCl3 tower vacuum is evaporated under reduced pressure after reaction, is steamed
Temperature is evaporated for 30-100 DEG C, and mixture intermediate, a substitution of POCl3 and dibasic mixture are obtained after vacuum distillation,
The ratio of mixture is 4:6, gas phase analysis, obtain mixture intermediate, the yield 95% of intermediate, the rate of recovery of POCl3
For 95%（Calculated with POCl3）.
Mixture intermediate is added in four-hole boiling flask, adds magnesium chloride 0.1g, first adds part hydroquinones 80g, is delayed
Slow to be warming up to 115-150 DEG C of reaction, the reaction time is 14 hours, and to after being released without hydrogen chloride, it is cold that reaction pours out liquid after terminating
But solidification is smashed, and the solid 100g after smashing is added into 150g water, is washed with the sodium hydroxide solutions of 30g 3%, then washed
Neutrality, material drying smashing obtain finished product, the total recovery about 80% of two-step reaction, fusing point：100-103 DEG C, triphenyl phosphate 5.0%,
Obtain white crystalline powder.
Embodiment 2：
Respectively by 160g（1mol）POCl3, titanium tetrachloride 1g, which is added in four-hole boiling flask, to be reacted, and it is 70-80 to rise to temperature
DEG C, phenol 94g (1mol) is slowly added dropwise, it is phenol time for adding about 2-3 hours, small in 80-90 DEG C of insulation reaction 3-5 after dripping
When, to after being released without hydrogen chloride, reaction is completed, and POCl3 is evaporated under reduced pressure after reaction, and vacuum is 30-100KPa, distillation
Temperature is 30-100 DEG C, and mixture intermediate, a substitution of POCl3 and dibasic mixture are obtained after vacuum distillation, is mixed
The ratio of compound is 5:5, gas phase analysis obtain mixture intermediate, the yield 95% of intermediate, and the rate of recovery of POCl3 is
95%（Calculated with POCl3）；
Mixture intermediate is added in four-hole boiling flask, adds titanium tetrachloride 1g, part hydroquinones 100g is first added, slowly rises
For temperature to 130-140 DEG C of reaction, the reaction time is 4-6 hours, to after being released without hydrogen chloride, is evaporated under reduced pressure deacidification, vacuum 30
- 100KPa, decompression temperature are 85-90 DEG C, decompression deacidification 1 hour, triethylamine 50g are slowly added dropwise, and feed liquid is neutrality, is added remaining
Hydroquinones 65g reacted, reaction temperature is 90-100 DEG C, and the reaction time be 3-4 hours, and liquid phase detects intermediate reaction
Completely.Reaction is poured out liquid cooling solidification and smashed after terminating, the solid 100g after smashing is added into 300g water, with the hydrogen of 100g 3%
Sodium hydroxide solution is washed, and then washing is neutral, and material drying smashing obtains finished product, the total recovery about 94% of two-step reaction, melts
Point：100-103 DEG C, triphenyl phosphate 0.5%, obtain white crystalline powder.
Comparative experimental example 2
Respectively by 160g（1mol）POCl3, titanium tetrachloride 1g, which is added in four-hole boiling flask, to be reacted, and it is 70-80 to rise to temperature
DEG C, phenol 94g (1mol) is slowly added dropwise, it is phenol time for adding about 2-3 hours, small in 80-90 DEG C of insulation reaction 4-5 after dripping
When, to after being released without hydrogen chloride, reaction is completed, and it is 30-100KPa that POCl3 tower vacuum is evaporated under reduced pressure after reaction, distillation
Temperature is 30-100 DEG C, and mixture intermediate, a substitution of POCl3 and dibasic mixture are obtained after vacuum distillation, is mixed
The ratio of compound is 5:5, gas phase analysis obtain mixture intermediate, the yield 95% of intermediate, and the rate of recovery of POCl3 is
95%（Calculated with POCl3）；
Mixture intermediate is added in four-hole boiling flask, adds titanium tetrachloride 1g, part hydroquinones 165g is first added, slowly rises
Temperature is to 115-145 DEG C of reaction, and the reaction time is 4-10 hours, and to after being released without hydrogen chloride, reaction pours out liquid cooling after terminating
Solidification is smashed, and the solid 100g after smashing is added into 300g water, is washed with the sodium hydroxide solutions of 100g 3%, then washed
Neutrality, material drying smashing obtain finished product, the total recovery about 84% of two-step reaction, fusing point：100-103 DEG C, triphenyl phosphate 5.5%,
Obtain white crystalline powder.
Embodiment 3：
Respectively by 1600g（1mol）POCl3, alchlor 10g, which is added in four-hole boiling flask, to be reacted, and it is 70- to rise to temperature
80 DEG C, phenol 1120g (1.1mol) is slowly added dropwise, it is phenol time for adding about 2-3 hours, anti-in 80-90 DEG C of insulation after dripping
Answer 3-5 hours, to after being released without hydrogen chloride, reaction is completed, be evaporated under reduced pressure after reaction POCl3 tower vacuum be 30-
100KPa, vapo(u)rizing temperature are 30-100 DEG C, and mixture intermediate, the substitution and two substitutions of POCl3 are obtained after vacuum distillation
Mixture, the ratio of mixture is 4:6, gas phase analysis, obtain mixture intermediate, the yield 95% of intermediate, POCl3
The rate of recovery be 95%（Calculated with POCl3）.
Mixture intermediate is added in four-hole boiling flask, adds alchlor 10g, first adds part hydroquinones 1000g,
130-145 DEG C of reaction is to slowly warm up to, the reaction time is 4-6 hours, to after being released without hydrogen chloride, is evaporated under reduced pressure deacidification, vacuum
It is 85-90 DEG C to spend for 30-100KPa, decompression temperature, decompression deacidification 1 hour, triethylamine 500g is slowly added dropwise, and feed liquid is neutrality,
Add remaining hydroquinones 650g to be reacted, reaction temperature is 90-100 DEG C, and the reaction time is 3-4 hours, and liquid phase detects
Intermediate reaction is complete.Reaction is poured out liquid cooling solidification and smashed after terminating, the solid 100g after smashing is added into 300g water, used
The sodium hydroxide solutions of 100g 3% are washed, and then washing is neutral, and material drying smashing obtains finished product, the total recovery of two-step reaction
About 94%, fusing point：100-103 DEG C, triphenyl phosphate 0.5%, obtain white crystalline powder.
Embodiment 4：
Respectively by 80g（0.5mol）POCl3,70g (1.5mol) phenol, butyl titanate 0.1g are added in four-hole boiling flask and carried out
Reaction, reaction temperature are 70-80 DEG C, are reacted 6 hours, and POCl3, vacuum 40-60KPa, distillation are evaporated under reduced pressure after reaction
Temperature is 80-90 DEG C, mixture intermediate after vacuum distillation, a substitution of POCl3 and dibasic mixture, mixture
Ratio be 4:6, gas phase analysis.
Mixture intermediate is added in four-hole boiling flask, adds titanium tetrachloride 1g, first adds part hydroquinones 100g, is delayed
Slow to be warming up to 130-140 DEG C of reaction, the reaction time is 5 hours, and detection hydroquinones is evaporated under reduced pressure deacidification, vacuum after having reacted
For 30-60KPa, decompression temperature is 85-90 DEG C, decompression deacidification 2 hours, triethylamine 6g is slowly added dropwise, and feed liquid is neutrality, is added
Remaining hydroquinones 65g is reacted, and reaction temperature is 85-100 DEG C, and the reaction time is 3-4 hours, and liquid phase detects intermediate
Reaction is complete.Reaction is poured out liquid cooling solidification and smashed after terminating, the solid 105g after smashing is added into 150g water, with 3g 3%
Sodium hydroxide solution is washed, and washing is neutral, and material drying smashing obtains finished product.Total recovery：94%, fusing point：100-103 DEG C, phosphorus
Triphenyl phosphate ester 0.9%, obtains white crystalline powder.
Example 5：
Respectively by 88g（0.55mol）POCl3, magnesium chloride 0.5g, which is added in four-hole boiling flask, to be reacted, and 94g (1mol) is added dropwise
Phenol, reaction temperature are 70-80 DEG C, are reacted 6 hours, and it is 40-60KPa that POCl3 tower vacuum is evaporated under reduced pressure after reaction, is steamed
Temperature is evaporated for 80-90 DEG C, and mixture intermediate after vacuum distillation, the one of POCl3 substitutes and dibasic mixture, mixing
The ratio of thing is 4.5:5.5, gas phase analysis.
Mixture intermediate is added in four-hole boiling flask, titanium tetrachloride 1g is added, hydroquinones 100g, is to slowly warm up to
130-140 DEG C of reaction, reaction time are 4 hours, and detection hydroquinones is evaporated under reduced pressure deacidification after react, vacuum for 30-
60KPa, decompression temperature are 85-90 DEG C, decompression deacidification 30 minutes, triethylamine 6g are slowly added dropwise, and feed liquid is neutrality, is added remaining
Hydroquinones 60g is reacted, and the reaction time is 3-4 hours, and reaction temperature is 85-100 DEG C, and liquid phase detection intermediate reaction is complete
Entirely.Reaction is poured out liquid cooling solidification and smashed after terminating, the solid 100g after smashing is added into 150g water, with the hydroxides of 3g 3%
Sodium solution is washed, and washing is neutral, and material drying smashing obtains finished product.Total recovery：94%, fusing point：100-103 DEG C, phosphoric acid triphen
Ester 1.0%, obtains white crystalline powder.
In terms of contrast test, using product made from the preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants
In, the content of toxicant triphenyl phosphate greatly reduces, and the time reacted shortens, and product quality is stable.
Claims (10)
1. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that by POCl3 and phenol
Reaction is carried out under lewis acid catalyst effect and prepares mixture intermediate, and mixture intermediate enters with part hydroquinones again
Row condensation reaction, high vacuum removing hydrogen chloride, adds organic base and remaining right after hydroquinones reaction completely after having taken off
Benzenediol carries out condensation reaction at low temperature, and after reaction terminates, cooling, solidification obtain crude product, and crude product, which crushes, to be post-processed through washing,
Washing is neutralized, drying obtains the low triphenyl phosphate engineering plastics halogen-free flame retardants of finished product, and its chemical equation is as follows：
,
0≤n≤6 in above formula, n=1 therein, 2,3,4,5,6 finished product contain different contents, and the weight/mass percentage composition of n=0 is less than
1%。
2. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, its feature
It is to comprise the following steps：
1）Esterif iotacation step：POCl3 and phenol are subjected to esterification to without hydrogen chloride under the catalysis of lewis acid catalyst
Untill releasing, remove under reduced pressure and reclaim POCl3, obtain a substitution of POCl3 and dibasic mixture intermediate；
2）Condensation polymerization step：Under the catalysis of lewis acid catalyst, first plus part hydroquinones is added to step 1）It is mixed
To close and primary condensation polymerisation is carried out in intermediate, the content for detecting hydroquinones extremely reacts complete, dehydrochlorination under vacuum, then
Add organic base and remaining hydroquinones progress secondary condensation polymerisation complete to intermediate reaction is mixed, obtain being esterified thick production
Thing；
3）Purification step：By step 2）Obtained esterification crude product is through cooling down, solidifying, pulverization process, and the product after crushing is through water
Wash, alkali cleaning, washing, drying obtain the low triphenyl phosphate engineering plastics halogen-free flame retardants of finished product.
3. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 2, its feature
It is step 1）In esterification reaction temperature be 80-90 DEG C, preferably 85-90 DEG C, the reaction time is 3-10 hours, preferably 4-6
Hour.
4. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 2, its feature
It is step 1）The molar ratio of middle POCl3 and phenol is 1：0.8-1.5, preferably 1:1 is evaporated under reduced pressure except remaining few
The temperature for measuring POCl3 is 90~120 DEG C, and preferably 85-90 DEG C of vacuum is 30~60KPa.
5. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 2, its feature
It is step 1）With step 2）In lewis acid catalyst be respectively titanium tetrachloride, alchlor or magnesium chloride, preferably chlorine
Change magnesium, catalyst amount for POCl3 weight 0.001-0.5%, preferably 0.01%.
6. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 2, its feature
It is step 2）In the molar ratio of mixture intermediate and total hydroquinones be 1：1.1-2.0 preferably 1：1.5 rub
You, the hydroquinones that puts into accounts for the 55-65% of total amount when primary condensation polymerize, and preferably 60%, what secondary condensation was put into when polymerizeing
Hydroquinones accounts for the 35-45% of total amount, preferably 40%, and primary condensation polymeric reaction temperature is 100~150 DEG C, and preferably 140
DEG C, it is 3-10 hours, preferably 3-5 hours once to integrate polymerization time.
7. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 2, its feature
It is step 2）Middle dehydrochlorination temperature is 60~100 DEG C, and preferably 65-90 DEG C, vacuum is 30~60KPa.
8. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 2, its feature
It is step 2）In organic base be triethylamine, diethylamine, ammonia or pyridine, preferably triethylamine, the amount for adding organic base is
The 2-5% of body weight among mixture, preferably 2%.
9. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 2, its feature
It is step 2）In remove de-chlorine hydride after secondary condensation polymeric reaction temperature be 60~100 DEG C, preferably 80-90 DEG C, reaction
Time is 4-13 hours, preferably 4-10 hours.
10. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 2, its feature
It is step 3）Middle to use alkaline weak solution alkali cleaning, alkaline weak solution is sodium hydroxide solution, sodium carbonate liquor or sodium acid carbonate
Any one in solution, preferably sodium hydroxide solution, the mass concentration 3~5% of alkaline weak solution, alkali cleaning temperature is 60~
80 DEG C, the alkali cleaning time is 25-35min, preferably 30min, separates water, is then washed to neutrality.
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| CN111205652A (en) * | 2020-03-18 | 2020-05-29 | 临海市奇升橡塑制品有限公司 | Modified flame retardant, high-temperature-resistant flame-retardant silicone rubber using flame retardant and application of silicone rubber |
| CN111205652B (en) * | 2020-03-18 | 2022-02-18 | 临海市奇升橡塑制品有限公司 | Modified flame retardant, high-temperature-resistant flame-retardant silicone rubber using flame retardant and application of silicone rubber |
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| CN113185547A (en) * | 2021-04-25 | 2021-07-30 | 山东卓俊实业有限公司 | Preparation method of compound with flame retardant property |
| CN113185547B (en) * | 2021-04-25 | 2022-05-20 | 广州银塑阻燃新材料股份有限公司 | Preparation method of compound with flame retardant property |
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